Polyfluorinated esters of acids containing silicon and amino groups

ABSTRACT

Polyfluorinated esters of the formula WHEREIN Rf is a polyfluorinated hydrocarbon radical containing at least three fluorine atoms and up to 20 carbon atoms, A is an alkylene radical of up to six carbon atoms, Z is the residue of an amine component selected from the group consisting of amines and amine slats which have had at least one hydrogen atom removed, and q is an integer selected from 1 and 2, useful as textile finishing agents.

United States Patent 11 1 Tesoro et a].

[54] POLYFLUORINATED ESTERS OF 1 ACIDS CONTAINING SILICON AND AMINOGROUPS [75] Inventors: Giuliana C. Tesoro, Dobbs Ferry,

N.Y.; Richard Ring, Wood-Ridge,

[73 A ssignee: J. P. Stevens & (20., Inc., New York,

[22] Filed: Nov. 27, 1967 [21] Appl. No.: 685,946

Related U.S. Application Data [63] Continuation-impart of Ser. No.178,572, March 9,

1962, Pat. No. 3,575,961.

[52] U.S. Cl ..260/448.8 R, 8/116.2 R, 8/128 R, 117/123 D, 117/1355,260/239 E, 260/295 R, 260/468 R, 260/479 S, 260/482 R,

260/633 [51] Int. Cl ..C07c 101/20, C07d 23/06, C07f 7/13 [58] Field ofSearch ..260/239 E, 448.8, 448.2

[ 5] March 6, 1973 [56] References Cited UNITED STATES PATENTS 3,504,9984/1970 Speier ..260/448.8 3,457,349 7/1969 Jelinek ..260/239 E PrimaryExaminer-Alton D. Rollins Attorney-J. Bradley Cohn and Bernard Marlowe[57] ABSTRACT Polyfluorinated esters of the formula RrOCA qZ 4 Claims,No Drawings POLYFLUORINATED ESTERS OF ACIDS CONTAINING SILICON AND AMINOGROUPS This application is a continuation-in-part of our copendingapplication Ser. No. 178,572, filed Mar. 9, 1962, now US. Pat. No.3,575,961.

This invention relates to polyfluorinated nitrogencontaining esterswhich are useful inter alia as finishing agents or intermediates forpreparing finishing agents.

More particularly, this invention concerns the abovementioned esterswhich can be employed as oil and water repellents, soil or stainreleasing agents, as intermediates for preparing these agents, and asacrylate donors of improved solubility for modifying cellulose and wool.

The novel compositions of this invention are included within the formu la V wherein R, is a polyfluorinated hydrocarbon radical containing atleast three fluorine atoms and up to carbon atoms, preferably selectedfrom aliphatic and aromatic radicals; A is an alkylene radical of up tosix carbon atoms; Z is a residue of an amine or amine salt after atleast one or two hydrogens have been removed, and q is either theinteger l or 2.

While all of the above compounds are useful, as in any large group, somemembers of the group are preferred compared to the group at large. Inthis instance the preferred group comprises those compounds representedin the structural formula where R; is polyfluorinated aliphatic radicalshaving from three to 11 carbon atoms and six to 21 fluorine atoms. Thesecompositions are useful finishing agents and can be prepared readilyfrom available materials.

It is an object of this invention among others to prepare useful novelpolyfluorinated esters containing at least three fluorine atoms and nomore than one nitrogen atom per molecule.

A more specific object of this invention is the preparation of the aboveesters useful as organic intermediates and as intermediates for thepreparation of textile finishing agents such as soil release agents andoil and water repellents.

Further objects will become apparent to those skilled in the art after aperusal of this invention.

In practice the above objects are achieved by the utilization of theaforementioned esters formed by several different processes.

In one process, an acrylic-type ester of a polyfluorinated alcohol isdirectly reacted with an amine containing at least one reactive hydrogenatom. Addition takes place across the site of unsaturation as shown bythe illustrative reactions below:

A'Jn be seerifrom an examination of the above illustrative embodiments,both aliphatic and aromatic polyfluorinated unsaturated esters lendthemselves to the preparation of the inventive products by the describedprocess. Similarly, the amine reactant can be acyclic, carbocyclic orheterocyclic. Furthermore, the chain as well as the ring may contain oneor more heteroatoms (as oxygen or silicon). Branching and/orunsaturation may occur.

A list of illustrative amines and amine salts which can be employed isas follows:

A list of illustrative polyfluorinated unsaturated esters which can beemployed is supplied below:

mas stave raiymiariaateanssmaea Esters 0 o racnco iicH=cHg, F3c2c0ii-cH:cH1,

l V l i I? (FsC)zCOC-C=CH, (F;C)1C-OCC=CH:,

III OH; T (:HP

0 o no no rictrz-oiicnalcm, 11 0 no mmxnoiimnxnn,

monoluncrnoommn, F CGUOi Cll Cflq C3115 CH3 I I (mamas,

is first formed, which upon addition of the fluorinated alcoholesterfies the alcohol to form the desired fluorinated, unsaturatedester.

Another more indirect procedure to prepare the unsaturated esterreactants is resorted to when the desired ester is to be synthesizedfrom a polyfluoro alcoholin which halogen and hydroxyl are attached tothe same acryloyl chloride to undergo metathesis to form the desiredester and cesium salt as the by-product.

In another procedure used to prepare the inventive composition, a moreindirect preparative method is a saturated employed. In one favoredvariant,

polyfluorinated ester halide of the type r RJOCAX wherein R, and A areas defined previously and X is a reactive halogen, is formed and reactedwith an amine or amine salt of the type described supra, to give theinventive products.

ll H(CFz)aCH2OCCH2CHzN During the course of this procedure ahalopropionic acid such as 3-chloropropionic acid is reacted with apolyfluorinated anhydride such as trifluoroacetic anhydride to form the3-chloropropionic trifluoroacetic anhydride, which is then reacted insitu with a polyfluorinated alcohol of the type:

R AOH patent of Hollander et al., US. Pat. No. 3,177,185 (1965).

Suitable illustrative polyfluorinated alcohols include the following:

tafluoropropionic trifluoroacetic anhydride.

To illustrate the workings of this invention in the greatest possibledetail, the following illustrative embodiments are submitted. Precedingthe examples is a brief description of the test methods used.

TEST METHODS AND WORKING EXAMPLES Vinyl, CH =CH: Determined by means ofl dodecanethiol according to the procedure described on page 61 ofChemistry of Acrylonitrile (The American Cyanamid Company, New York,1959, second edition). For the determination of a water-soluble vinylcompound, the reagent was 2-mercaptoethanol in the presence of excessbase.

Water Repellency Spray Rating: AATCC Test Method 22-l 964, Manual of theAmerican Association of Textile Chemists and Colorists, 1964 edition,pages B-l30-31.

Durability to Laundering: Home-type machine, low (ll-gallon) waterlevel, 4-pound load, detergent, normal agitation, 12-minute wash cycleat 60 C, rinse at 43 i 3 C, normal rinse and spin cycle, and tumble-dryat 74 C.

Durability to Dry Cleaning: Commercial equipment and formulation.

Oil Repellency: Swatches of fabric were placed flat on a table, withedges held down by weights. Drops of mineral oil were placed onto thesurface of the fabric at various places, and the effect was observed.Oil repellency was shown if no penetration, wetting, or darkeningoccurred as the drops remained undisturbed for 3 minutes. Specificationson the mineral oil: Saybolt Viscosity of 360 to 390 at F (377/9 C) and aspecific gravity of 0.880 to 0.900 at 60 F (155/9 C). Oil and WaterRepellent Concentration: An oil and water repellent concentration asused herein refers to that quantity of polyfluorinated ester reagentwhich will prevent substantial penetration of the glass or cellulosicsubstrate by oil or water. This concentration is a variable dependentupon the type of substrate to be protected and the reagent employed.Experimentally it has been determined that satisfactory repellency canordinarily be obtained at concentrations of reagents ranging from about0.1 percent by weight of reagent and above based upon the weight ofsubstrate to be protected. Preferably, the reagent applied will be inthe concentration range of from about 0.5 percent by weight and abovebased upon the weight of the substrate. The upper limit of theseconcentrations is primarily limited by costs.

OWB: On the weight of the bath. OWF: 0n the weight of the fabric.

EXAMPLE 1 Preparation of 1H,1H'Pentadecafluoroocty1 Acrylate i? [F 0 C]0 Acrylic acid grams, 0.14 mole) was cooled to 10 C in a 250-ml. flask.While stirring, a total of 30 grams (0.14 mole) of trifluoroaceticanhydride was added dropwise at 10 to C. Then a total of 50 grams (0.11mole) of 1H,ll'l-pentadecafluoro-l-octanol was added dropwise while thetemperature was kept below 30 C. Upon completion of the addition, thereaction mixture was stirred for 2 hours at room temperature. Next, atotal of 30 ml. of water was added slowly with stirring while thetemperature was kept below 50 C. Finally the mixture was allowed toseparate into layers. The lower layer was isolated and distilled. Thefraction distilling between 53 and 56 C at 2 torrs weighed 42 grams. Ithad a vinyl content of 5.92 percent by analysis. The vinyl contenttheoretically required for 111,1 l-l-pentadecafluorooctyl acrylate is5.95 percent.

EXAMPLE 2 Preparation of 1H,ll-l-Pentadecafluorooctyl 3- A total of 67.2grams (0.32 mole) of trifluoroacetic anhydride was added slowly withstirring to 33.6 grams (0.3] mole) of 3-chl0ropropionic acid kept justbelow 15 C in a 250-ml., 3-neck flask equipped with a dropping funnel,stirrer, and thermometer. The reaction mixture was stirred at 10 to 15 Cfor 15 minutes after all the anhydride had been added in order to allowfor completion of the formation of 3-chloropropionic trifluoroaceticanhydride. Then a total of 120 grams (0.30 mole) of molten1H,ll-l-pentadecafluoro-1-octanol was added while the temperature waskept between 10 and 30 C. Upon completion of the addition, the reactionmixture was stirred for 2 hours at 25 .to 30 C. Next, the reactionmixture was cooled to 10 C, and a -ml. portion of cold water was addedwhile the temperature was kept just below 15 C. Then stirring wasstopped and the mixture separated into layers. The lower layer wasseparated. The operation of adding a 75-ml. portion of cold water wasrepeated two times on the lower layer. The final lower layer was dilutedwith 250 ml. of ethyl ether, then dried by standing 16 hours overanhydrous sodium sulfate. After filtering to remove the drying agent,the liquid was subjected to fractional distillation at reduced pressure.The 3- chloropropionate of 1H,lH-pentadecafluoro-l-octanol was collectedbetween 62 and 66 C at 0.1 torr. The distilled ester weighed 86 grams.The identity of the product was confirmed by the infrared spectrum andby the following analytical values.

Preparation of l- 2-[(1H,lH-Pentadecafluorooctyloxy)carbonyl]ethyl-pyridinium Chloride The following compounds were measured into a 250-ml. 3-neck flask fitted with a thermometer, stirrer, and refluxcondenser: 24.5 grams (0.05 mole) of lI-1,ll-lpentadecafluorooctyl3-chloropropionate,4.0 grams (0.0506 mole) of pyridine, and 50 ml. ofmethanol. The mixture was stirred and heated to refluxing for a total of63 hours, by which time the reaction had gone 67 percent to completion,based on the determination of chloride ion. Methanol and unreactedpyridine were removed by distillation at approximately 25 torrs whilethe mixture was kept at 45 C. The resulting product, 21 grams, mainly 1-2-[(1H,1H-pentadecafluorooctyloxy)carbonyl]ethyl -pyridinium chloride,gave the following results upon analysis: chloride ion, 4.18 percent;latent vinyl corresponding to an actual vinyl content of 6.25 percent.(Vinyl content was determined by means of 2-mercaptoethanol in thepresence of excess base.) The adduct, a quaternary ammonium salt, wasvery soluble in water, despite the pentadecafluorooctyl moiety in thecation. This product is useful as an acrylate donor (for chemicallybonding pentadecafluorooctyl through a bridging group to cellulose orwool) because of its solubility property.

EXAMPLE 4 Preparation of ll-l,ll-l-Pentadecafluorooctyl 3-( 1-Aziridinyl)propionate F (CF)1cH1Oc' oH cn, nxr; 11 cm 1*(0 whom-0rcmcmsorm m,

1 weighed 9.4 grams. It had a nitrogen content of 2.40

percent (2.82 percent by theory). The infrared spectrum confirmed thatthe adduct was 1H,1H-pentadecafluorooctyl 3-( l-aziridinyl)propionate.Titration with hydrochloric acid indicated an aziridinyl content of 7.05percent (8.48 percent by theory).

EXAMPLE 5 The following compounds were measured into a 125- ml. flaskequipped with a magnetic stirrer: 9.08 grams (0.02 mole) of1H,1l-l-pentadecafluorooctyl acrylate and 30 ml. of ethyl ether.Stirring was started, and a solution of 2.21 grams (0.01 mole) of3-(triethoxysilyl)-propylamine in 20 ml. of ethyl ether was added.Stirring was discontinued, the flask was corked, and the solution wasallowed to stand at room temperature for approximately 16 hours. Ethylether and other volatile material were removed by distillation. Theremaining viscous liquid weighed 10.5 grams. It had a nitrogen contentof 1.35 percent (1.24 percent by theory) and an infrared spectrum whichconfirmed that the adduct was bis( 1H 1 l-l-pentadecafluorooctyl) N-[S-(triethoxysilyl )propyl]-3 ,3 -iminodipropionate.

Preparation of Acrylate H020 CH=CH Acrylic acid 15.1 grams, 0.21 mole)and 0.1 gram of hydroquinone (to inhibit polymerization) were put into a250-ml. flask fitted with a stirrer, a dropping funnel, and athermometer. While stirring and cooling, a total of 46.2 grams (0.22mole) of trifluoroacetic anhydride was added portionwise at to C. Then atotal of 106.4 grams (0.20 mole) of1H,1l-l,l1l-l-eicosa.fluorol-undecanol was added while the temperaturewas kept below 30 C. Upon completion of the addition, the reactionmixture was stirred for 2 hours at room temperature. Next, a total of 50ml. of water was added slowly with stirring while the temperature waskept below 15 C. Some solidification occurred, so a 250-ml. portion ofethyl ether was added. The organic layer was washed with -ml. portionsof 5 percent sodium carbonate until an added portion remained pink tophenolphthalein. Then the organic layer was washed with water and driedover anhydrous magnesium sulfate. Solvent was removed by distillation.That left the ester as a white solid. It was recrystallized from alcoholto which water was added. The product weighed 75.5 grams and melted at44.0 to 445 C. It had a vinyl content of 4.60 percent by analysis. Thevinyl content theoretically required for 1H,1H,1 lH-eisosafluoroundecylacrylate is 4.68 percent.

EXAMPLE 7 Preparation of 1H,1H,llH-Eicosafluoroundecyl 3-Chloropropionate o I ll H020 0112011201 Frag-0430112011291 A total of46.2 grams (0.22 mole) of trifluoroacetic anhydride was added slowlywith stirring at 10 to 15 C to 22.8 grams (0.21 mole) of3-chloropropionic acid in a 500-ml. flask. After the addition, thereaction mixture 7 was stirred for 15 minutes (still at 10 to 15 C) toallow for completion of the formation of 3-chloropropionictrifluoroacetic anhydride. Then, a total of 106.4 grams was added, andstirring was continued for an additional period of 3 hours, during whichtime the temperature was allowed to rise to 29 C as the ester formed.Next, the reaction'mixture was cooled to 15 C, and a 250-ml. portion ofcold water was added. After the mixture had been stirred for 15 minutes,the white precipitate was collected by filtration. The product wasdissolved in ethanol, and recrystallized from aqueous ethanol. The yieldof 1H l H, 1 ll-l-eicosafluoroundecyl 3- chloropropionate was 93 grams(76 percent yield) melting at 60-61 C. The identity of this ester wasestablished by its infrared spectrum and the following analyticalresults.

c 11 c1 F Analysis (in Found: 26.03 1.25 5.27 57.69

Required for c,.1-1,c11-',,0,= 27.00 1.13 5.70 61.22

EXAMPLE 8 Preparation of 1-[2-( ll-l,1l-l,1 ll-l-Eicosafluoroundecyloxy)ethyl]-pyridinium Chloride of 63 hours, by which time the reaction hadgone 66 percent to completion, based on the amount of chloride ionproduced. Methanol and unreacted pyridine were removed by distillationat approximately 25 torrs while the mixture was kept warmed at roomtemperature. The resulting product, 28 grams, mainly l-[ 2( 1l-1,1H,l1l-l-eicosafluoroundecyloxy)ethyl] pyridinium chloride, gave thefollowing results upon analysis: chloride ion, 3.33 percent; latentvinyl corresponding to an actual vinyl content of 4.33 percent. (Vinylcontent was determined by means of 2-mercaptoethanol in the presence ofexcess base.) The adduct, a quaternary ammonium salt, was a waxy solid,virtually insoluble in water because of the eicosafluoroundecyl moietyin the cation.

EXAMPLE 9 Preparation of 1l-1,1H,1ll-l-Eicosafluoroundecyl 3-1-Aziridinyl)propionate H(CFz)1uCH2O|1|}CH=CH 11mm mornmoirroocnzommrrzThe addition reaction was effected with the following compounds, usingthe apparatus and procedure of EX- AMPLE 4: 11.72 grams (0.02 mole) of1H,1H,11H- eicosafluoroundecyl acrylate in 40 ml. of ethyl ether, and0.86 gram (0.02 mole) of ethylenimine. The adduct obtained weighed 12.5grams, a virtually quantitative yield. It was a waxy solid; N: found,2.4 percent; required for C H F NO 2.1 percent. Titration withhydrochloric acid indicated an aziridinyl content of 5 .98 percent (6.68percent by theory), confirming that the adduct was the ester, 1H,ll-l,1lH-eicosafluoroundecyl 3-( 1-azirdinyl)propionate.

EXAMPLE EXAMPLE 1 1 Preparation of lH,ll-l,7H-Dodecafluoroheptyl 2-(1-Aziridinyl)propionate This compound was prepared from ethylenimine and1H,lH,71-l-dodecafluoroheptyl acrylate by the procedure outlined inEXAMPLE 9. The product obtained was purified by distillation. Yield 88%,hp 78-92 C/O.4mm. Equivalent weight determined by potentiometrictitration: Calcd.: 429; Found: 460.

EXAMPLE 12 Preparation of Bis( 1H,1H,l ll-I-eicosafluoroundecyl) N3-(Triethoxysily1)propyl ]-3 ,3 -iminodipropionate 2mm meur-oficumiomumomomon,sic-00,115

EXAMPLE 13 Preparation of (trifluoromethyl)ethyl Acrylate2,2,2-Trifluoro- 1 FaCCO2H A solution consisting of grams of 96percentpure acrylic acid and 0.8 gram of hydroquinone was added slowlyto 454 grams of trifluoroacetic anhydride at 0 to 10 C in a 2-1iter3-neck flask fitted 'with a thermometer, stirrer, and dropping funnelwith a drying tube. Then a total of 330 grams of 2H-hexafluoro-2-propanol was added while the temperature was kept between 10 and 20 C.Upon completion of the addition, the reaction mixture was stirred for1.5 hours at 25 to 30 C and for an additional 2 hours at 40 C. Next, thereaction mixture was cooled to 0 C, and a total of 0.5 liter of coldwater was added during a period of 20 minutes while the temperature waskept at 10 C. Then stirring was stopped and the mixture separated intolayers. The lower layer was isolated and diluted by 0.5 liter ofdichloromethane. That solution was washed by five 150-ml. portions ofwater, and then dried by standing over anhydrous sodium sulfate.Approximately 0.1 gram of hydroquinone was added to the dry liquid(separated from the drying agent), and the liquid was subjected tofractional distillation at reduced pressure. The acrylate of2H-hexafluoro-2- propanol was collected between 38 and 42 C at 140torrs. The normal boiling point was approximately 88 C. The distilledester weighed grams (40 percent of the theoretical yield). The infraredspectrum confirmed the identity of this ester.

EXAMPLE 14 Preparation of 2,2,2-Trifluoro- 1 (trifluoromethyl)ethyl3-Chloropropionate I H (FaChC-OCCHzCIhCl A total of 51.6 grams of3-chloropropionic acid was added slowly with stirring to 100 grams oftrifluoroacetic anhydride at C in a 500-ml. flask fitted with athermometer, stirrer, and a dropping funnel with a drying tube. Then thetemperature was raised to 10 C, and 2l-l-hexafluoro-2-propanol was addeddropwise with stirring. Upon completion of the addition, the reactionmixture was stirred for 5 hours as the temperature rose gradually to 40C. The reaction mixture was cooled to 0 C, and a total of 100 ml. ofwater was added slowly with stirring while the temperature was keptbelow C. Finally the mixture was allowed to separate into layers. Thelower layer was isolated. It was washed with five 50-ml. portions ofcold water, and dried by standing over anhydrous sodium sulfate. The dryliquid was fractionally distilled at reduced pressure. The3-chloropropionate of 2l-l-hexafluoro-2-propanol was collected at 61 Cat 40 torrs; 54.1 grams (48.5 percent yield).

Using apparatus and general procedure both similar to those of EXAMPLE4, an addition reaction was carried out with the following compounds:11.1 grams (0.05 mole) of the acrylate of 2l-l-hexafluoro-2- propanoldissolved in 30 ml. of ethyl ether, and 5.0 grams (0.05 mole) ofdiallylamine dissolved in 20 ml.

of ethyl ether. After processing, the yield of the3-(diallylamino)propionate of 2l-l-hexafluoro-2-propanol which distilledbetween 46 and 47 C at 0.4 torr was 10.2 grams (63.3 percent). Thestructure of the adduct was confirmed by its infrared spectrum and bynitrogen content: found, 4.40 percent; required for C I-1 E, N0 4.39percent.

EXAMPLE 16 Preparation of 2,2,2-Trifluorol (trifluoromethyl)ethyl 3-(l-Aziridinyl)propionate Using a method similar to that of EXAMPLE 4(except that the time allowed was 4 days), an addition reaction wascarried out with the following compounds: 5.6 grams (0.025 mole) of theacrylate of 2l-l-hexafluoro-2-propanol dissolved in 30 ml. of ethylether, and 1.1 gram (0.025 mole) of ethylenimine dissolved in 20 ml. ofethyl ether. At the end of the reaction period, volatile compounds wereremoved by distillation at atmospheric pressure while the pottemperature was raised to 70 C. Then the 3-( l-aziridinyl)propionate of2H-hexafluoro-2-propan0l was isolated by distillation at reducedpressure as a fraction collected between 54 and 55 C at 10 torrs; n1.3541. The yield of the adduct was 5.0 grams (75 percent).

Aziri- C H F N dine Analysis (in Found: 36.11 3.53 38.90 6.55 14.3Required for C,,H.F,N0,= 36.24 3.42 42.99 5.28 15.9

* The method of determination used is described in Schaefer et al.,Journal American Chemical Society, Vol. 77, 5918-5922 (1955).

EXAMPLE 17 Using a method similar to that of EXAMPLE 4 (except that thetime allowed was four days), an addition reaction was carried out withthe following compounds: 5.6 grams (0.025 mole) of the acrylate ofZH-heirafluoro-2-propanol dissolved in 30 ml. of ethyl ether, and 2.8grams (0.0125 mole) of 3-(triethoxysily1)propylarnine dissolved in 20ml. of ethyl ether. At the end of the reaction period, volatile materialwas removed by distillation at atmospheric pressure while the pottemperature was raised to C. A quantitative yield was obtained of theadduct, the N-[3-(triethoxysily1)propyl]-3,3'-iminodipropionate of2l-l-hexafluoro-2-propanol, the structure being in accord with theinfrared spectrum. EXAMPLE 20 illustrates the usefulness of this newcomposition having the molecular formula C H ,F NO-,Si as awater-repellent finish for cotton fabric. The use of thispolyfluoroalkyl ester of N-substituted beta-alanine to increase oilrepellency of glass fabrics is shown in EXAMPLES 21 and 22.

EXAMPLE 18 Preparation of 1 ,2,2,2-' letrafluoro-2-(trifluoromethyl)ethyl Acrylate Cesium fluoride (126 grams, 0.75 mole)and 360 ml. of redistilled bis(2-methoxyethyl) ether were cooled to 78 Cin a l-liter, 3-neck round-bottom flask which had been flame dried andfitted with a condenser, stirrer, gas inlet tube, and thermometer. Atotal of 138 grams (0.84 mole) of hexafluoroacetone was bubbled into themixture. Then the mixture containing the cesium derivative ofheptafluoro-Z-propanol was warmed to room temperature and re-chilled to10 C. Acryloyl chloride (75.2 grams, 0.75 mole) was added dropwiseduring a 20-minute period. Next, the mixture was stirred for 1 hour atroom temperature, and for 1 hour at 50 C. It was cooled and filtered toremove cesium chloride. The filtrate, diluted by 250 ml. of ethyl ether,was poured into 1 liter of cold water. The lower layer C H F Analysis(in%). Found: 29.95 1.24 54.56 Required for C,,l-l- ,F-,O,: 30.00 1.2555.40

EXAMPLE 19 Use of the Adduct of EXAMPLE 12 as a Water- Repellent Finishon Cotton Fabric Four samples of 100 percent cotton fabric (8 ounces persquare yard in a twill weave) were conditioned with the relativehumidity at 65 i- 2 percent (21 2*: 1 C) and weighed to the nearestmilligram. Each sample was padded with a solution of bis(ll-l,lH,111-1-eicosafluoroundecyl) N-[3-(triethoxysilyl)propyl]-3,3'-iminodipropionate (the product of EXAMPLE 12, C H F NO Si) inbis(2-methoxyethyl) ether. The concentration of the reagent in the padbath was 5.0 percent for Samples K and L, and 1.8 percent for Samples Mand N. For each padding of the reagent, the wet pick-up was 62 percent.Other quantitative details are in the accompanying table.

The fabric samples were dried at approximately 50 C. Samples L and Nwere overpadded with an aqueous dispersion of a mixed catalyst, as notedin the table, and re-dried as before. The same curing conditions wereapplied to each sample, viz., 5 minutes at approximately 177 C. Nexteach sample was rinsed in bis(2- methoxyethyl) ether, and then in watercontaining approximately 0.1 percent of a nonionic detergent, namely p-(l l ,3 ,3-tetramethylbutyl)-phenoxynonaethoxyethanol. After drying, thesamples were re-conditioned and re-weighed as before. Even small amountsof the finish, an amine adduct of a polyfluoroalkyl acrylate, providedwater repellency, as shown in the table.

" TABLE FOR EXAMPLE m m trifluoro- 1 -(trifluoromethyl )ethyl] N-[ 3-(triethoxysily1)propyl]-3,3'-iminodipropionate (the product of EXAMPLEl7, C ,H F, NO Si) in p-dioxane. The concentration of the reagent in thepad bath was 4.0 percent for Samples A, B, C, D, and H, and 1.5 percentfor Samples E, F, and G. For each padding of the reagent, the wetpick-up was 62 i 1 percent. Other quantitative details are in theaccompanying table.

The fabric samples were dried at approximately 65 C. Samples B through Gwere overpadded with an aqueous dispersion of a catalyst, as noted inthe table. (Before using Catalyst 81 and 128, the pH of the aqueousdispersion was fixed at 6.5 i 0.5 by means of acetic acid if previouslyabove that range.) For Sample H, benzoyl peroxide was applied with thereagent from pdioxane. Samples of overpadded fabric were re-dried asbefore. The same curing conditions were applied to each sample, viz., 5minutes at approximately 177 C. Next, each sample was rinsed inbis(2-methoxyethyl) ether, and then in water. After drying, the sampleswere reconditioned and reweighed as before. Results in the table showthat the finish, an amine adduct of a polyfluoroalkyl acrylate, providedwater repellency.

TABLE FOR EXAMPLE 20 Reagent, Catalysts, OWB Water repelleneyC11H31F12N07Sl percent spray rating Organo- Metal tuncorg. After OWBOWF, tional, salt, Orlgllaunderpercent percent Type 81 Type 128 nallying Sample A 4. 0 2. 5 None None 50/70 0/60 4. 0 2. 5 0. 1 None 70 4. 02. 5 None 0. 6 70 50 D 4. 0 2. 5 0. 1 0. 6 50/70 70 E 1. 5 0. 9 0. 1None 70 50 F 1. 5 0.9 None 0.6 50/70 50/70 G 1. 5 0. 9 0. 1 0. 6 50/700/5() H 4. 0 2. 7 None None 50 50 Control (the untreated cotton fabric)0 0 Catalysts: See footnote to table for Example 19. "For Sample H,benzoyl peroxide (1.3% OWB) was applied with the reagent from p-dioxane.

EXAMPLE 21 Use of the Adduct of EXAMPLE 17 (Applied from Solution) as anOil-Repellent Finish on Glass Fabric A glass fabric was selected whichwas of a style popular for draperies, having a thread count of 56 X 54.The adduct of EXAMPLE l7, namely bis[2,2,2-trifluoro-l- Catalysts:Products 01 Dow Corning Corp. (50% solids and pyridine carrier for Type81; 28% solids [or Type 128). Wct pick-up from the aqueous pad bath wasapproximately EXAMPLE 20 Use of the Adduct of EXAMPLE 17 as a Water-Repellent Finish on Cotton Fabric Eight samples of percent cotton fabricof the type used in EXAMPLE 19, each 8 by 12 inches, were conditionedand weighed as described in that example. Each sample was padded with asolution of bis[2,2,2-

(trifluoromethyl )ethyl] N- 3-(triethoxysilyl )propyl3,3-iminodipropionate, was diluted to 5 percent in ethanol and appliedas a finish to the glass fabric by a 65 padding operation. That is, thecloth, impregnated with the solution, was squeezed as it passed betweentwo pad rollers. The wet pick-up was approximately 30 percent. Thepadded fabric was cut into seven specimens,

each of which was dried under a different set of conditions, asindicated in the accompanying table. For each set of drying conditions,the oil repeller of this invention was effective in the test inpreventing mineral oil from penetrating the fabric. Without the adduct,

mineral oil penetrated promptly. That is, the fabric had nooilrepellency prior to treatment with the addition compound made from3-(triethoxysilyl)propylamine and the acrylate of2H-hexafluoro-2-propanol.

Use of the Adduct of EXAMPLE l7 (Applied as Vapor) as an Oil-RepellentFinish on Glass Fabric The adduct of EXAMPLE l7, C H F No Si, wasapplied in the form of vapor (instead of being padded on) to aheat-cleaned, casement-style glass fabric. The equipment for vapor-phaseapplication consisted of an insulated chamber which could be heated to180 C. The glass fabric was draped over steel racks inside the chamber.A IO-ml. portion of the adduct of EXAMPLE 17 was allowed to drip from adropping funnel into the otherwise sealed chamber. Each drop struck ahot trough inside as the chamber and its contents were being heated at170 2': 10 C. The addition and vaporization were carried out atatmospheric pressure over a period of 15 minutes. Whereas a portion ofthe original (control) fabric was promptly penetrated by 16 mineral oil(i.e., the fabric had no oil repellency), the finish of this inventionprevented penetration or wetting of the treated fabric in the test foroil repellency, although the amount of C H F NO Si condensed on thefibers was of the order of only 0.01 percent of the weight of thefabric.

As the various examples and suggested embodiments indicate, numerouschanges can be made in reaction conditions and reactants withoutdeparting from the inventive concept. The metes and bounds of thisinvention are best indicated by the claims which follow.

What is claimed is:

1 Polyfluorinated esters of the formula 0 II (moccmcm momomcmsuo(1 inwherein R, is a polyfluorinated hydrocarbon radical free of olefinic oracetylenic unsaturation and containing at least three fluorine atoms andup to 20 carbon atoms. 2.

1. Polyfluorinated esters of the formula wherein Rf is a polyfluorinated hydrocarbon radical free of olefinic or acetylenic unsaturation and containing at least three fluorine atoms and up to 20 carbon atoms.
 2. 3. 